US1744109A - Process for converting hydrocarbon oils - Google Patents

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C P. DUBBS ETA! PROCESS FOR CONVERTING HYDROCARBON OILS Original Filed May 29 1922 (urban ffiazvba J cqaes GY/Iorrell.

. such as gasoline.

Patented Jan.. 21, 1930 UNITED STATES PATENT OFFICE.

CARBON 1. DUBBS, OF WILMETTE, AND JACQUE C. MORRELL, OF GHIOAG'O, ILLINOIS:

SAID DUBBS ASSIG-NOR TO UNIVERSAL OIL PRODUCTS COMPANY, OF CHICAGO, ILLINOIS, A CORPORATION OF SOUTH DAKOTA PROCESS FOR CONVERTING HYDROCARBON OILS Application filed May 29, 1922, Serial This invention relates to improvements in a process for the conversion of hydrocarbon oils, and refers more particularly to the production of light oils such as gasoline from relatively heavier oils.

Among the objects of the invention are to provide a process in which oils emulsified naturally or artificially with water, such as a California oil, are directly treated to produce lower boiling point oils; to provide a process in which the oil is treated in the presence of catalytic materials such as easily reducible metallic oxides; to provide a process which is preferably operated under pressure of the generated vapor, a process in which the catalyst is regenerated.

Fig. 1 is a diagrammatic side elevational view of the apparatus.

Fig. 2 is a plan view of a portion of the apparatus shown in Fig. 1.

The treatment of emulsified oils is particularly diflicult due to the presence of water which renders distillation of the oil almost impossible until the water has been driven out of the'oil body. The fact that the water is so thoroughly emulsified and dispersed through the oil produces innumerable difficulties in distillation. Frequent attempts have been made to crack these emulsified oils into gasoline, but the difficulties attending these methods rendered the ractical application-of the processes inopera 1e.

vapor acts as a ositive aid in the conversion of these emulsi ed petroleums to lighter oils,

The reason for this is in certain chemical reactions which take place between the water vapor and the catalysts. In the practical application of the present process, the oil is raised to a conversion temperature, and is distilled in tubes containing the catalytic material, or alternate methods of combining the oil while in the conversion state with the catalytic material may be racticed, such as passing; the emulsifie oil through heated coils, so that the vaporized oil will mix with the steam or water vapor orifinally present in the emulsified w oil as suc Referring to the drawings: The-oil to be preferably heated by means of gas burners 5.

N0. 564,349. Renewed August 3, 1928.

treated is introduced from any convenient extraneous source through the line 1, and is charged by means of the pump 2 to the heating coils 3 mounted in a furnace 4, which is The oil, after being raised to a conversion temperature under a substantial pressure of the generated gaseous vapors, is directed to the distilling zone or vaporizing chambers 6 and 7, which are connected to lines 8 and 9. The transfer line 10 through which the oil passes in its travel from the heating tubes to the vaporizing chambers terminates in the Y connection communicating with the pipes 8 and 9 controlled by valves 11 and 11 The distilling or vaporizing chambers are mounted in an oven or furnace arrangement 12 heated by burners 13 which serve to main tain the chambers at a desired temperature. A steam header 14 having secondary connections 15 and 16,- controlled by regulating valves 17 and 18 is connected to the vaporizing chambers, whereby steam may be introduced, if desired, to separate distilling tubes. The header 19 joining the chambers 6 and 7 is connected to vapor riser 2O controlled by a suitable valve which communicates with the de hlegmator 21, which in turnconnects throug line 22 to the water condenser 23. The condenser is connected throughline 25, controlled by valve 26 to receiver 27, the

v 4 latter being equipped with pressure relief In the present process the presence of water with the charging stock to the heating zone for retreatment. 5

In operation, the emulsified oil to be treated is introduced and raised to a conversion temperature in the heating zone a d then passes to the distilling or vaporizing chamber. The vaporizing chambers contain catalytic material such as ferric oxide or other oxides or compounds of metals shown at 41 which have a catalytic action when in the presence of the flowing oil body. The vapors evolved in the distilling chamber pass off through the riser and after being dephlegmated, are collected as distillate in the receiver. The presence of a catalytic material both improves the quality of the distillate and also gives an increased yield of low boiling point distillates.

Among the advantages of the process may be mentioned the ability to treat emulsified oil directly into gasoline, thus taking advantage of the water vapor which is otherwise a hindrance in carying out the reaction. The presence of the water vapor and catalyst with the oil body during its conversion seems to have a distinct advantage rather than being a hindrance in the conversion or cracking reaction. This is an advance in the art of treating what has heretofore been a very refractory petroleum product.

The presence of water vapor in the tubes containing the catalyst also prevents the formation of carbon and other substances deleterious to the reaction and allows every surface of the catalysts to come in contact with the treated oil vapors at all times. lVithout the presence of the water vapor there is a tendency of the precipitating carbon particles to collect upon the catalytic material and materially hinder and retard its effect upon the reaction of the oil. The distillate or product is of high quality owing to the presence of hydrogen in the system formed as a secondary reaction and as a consequence a good yield is obtained.

Control valves are situated in the transfer lines to the respective chambers and valves 42 and 43 in the header 19 for isolating either of the chambers so that they may be run alternately, one being opened for cleaning and blown out with steam if desired, while the other is in operation.

It has been found that if the ratio of oil to Water in the natural emulsified petroleum is greater than from 85 to 90 per cent, more water in the form of steam may be added, with a decidedly improved effect upon the flowing oil, thus supplying more water vapor and at the same time agitating the oil and producing a more even distribution of the emulsified oil. If the ratio is less than these figures, better results will be obtained if oil is supplied to an extent to raise the ratio to the figures mentioned. It is understood that it is not F., may be maintained during conversion. It is understood, however, that the method of operation and the form of the apparatus may be varied without departing from the spirit and subject matter of the invention.

We claim as our invention:

1. A continuous process for cracking emulsified oil, consisting in passing oil and water in an emulsified condition through a heating coil, wherein the emulsified material is raised to a conversion temperature, in transferring the highly heated material into an enlarged zone, wherein it is subjected to the action of a metallic oxide, and in maintaining the ratio of oil and water in the emulsion such that the oil represents from 85 to 95 per cent thereof.

2. A continuous process for cracking emulsified oil, consisting in passing the oil and water in an emulsified condition through a heating coil, wherein it is raised to a conversion temperature, in maintaining the ratio of oil to water such that the oil represents at least 85 per cent of the emulsion, by introducing additional water-free oil to the charging material for the process when the water content of the emulsion exceeds 15 per cent, in delivering the highly heated emulsified material to an enlarged zone, wherein it is subjected to the action of ferric oxide, in withdrawing unvaporized portions of the emulsion from said enlarged zone, and in separately taking off vaporized constituents from said enlarged zone for condensation and collection.

CARBON P. DUBBS. JACQUE C. MORRELL.

proposed to limit the process to these specific

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